Publication

Interfacial polymer architecture can control nanoparticle dispersion and rheological behavior of nanocomposites

Abstract

Polymer nanocomposites (PNCs) have become essential components in many advanced materials applications, from solid state battery electrolytes to high-performance structural components. In PNCs, the large fraction of interfacial polymers determines their outstanding rheological performance; yet, strategies to control the structure and dynamics of the interfacial polymer has been very limited. Here, using poly(ethylene oxide)-silica model nanocomposite system, we propose a facile approach based on varying macromolecular architecture of interfacial polymers. We show that by changing the topology of the bound polymer from linear to star and hyperbranched, polymer-NP interaction as well as chain interpenetration in the interphases can be effectively altered without changing type or molecular weight of the polymer, or NP surface chemistry in attractive PNCs. Our results show that both dispersion and rheological behavior of PNCs depend highly on functionality and arm length of the polymers used at the interfaces. These results can be used to design ion-conductive molten polymer electrolytes with significantly improved mechanical properties suitable for solid-state battery applications.

DOI

Miniaturized wireless sensor enables real-time monitoring of food spoilage

Abstract

Food spoilage results in food waste and food-borne diseases. Yet, standard laboratory tests to determine spoilage (mainly volatile biogenic amines) are not performed regularly by supply chain personnel or end customers. Here we developed a poly(styrene-co-maleic anhydride)-based, miniature (2 × 2 cm2) sensor for on-demand spoilage analysis via mobile phones. To demonstrate a real-life application, the wireless sensor was embedded into packaged chicken and beef; consecutive readings from meat samples using the sensor under various storage conditions enabled the monitoring of spoilage. While samples stored at room temperature showed an almost 700% change in sensor response on the third day, those stored in the freezer resulted in an insignificant change in sensor output. The proposed low-cost, miniature wireless sensor nodes can be integrated into packaged foods, helping consumers and suppliers detect spoilage of protein-rich foods on demand, and ultimately preventing food waste and food-borne diseases.

Emin İstif, Hadi Mirzajani, Çağdaş Dağ, Fariborz Mirlou, Elif Yaren Özüaçıksöz, Cengiz Çakır, Hatice Ceylan Koydemir, İskender Yılgör, Emel Yılgör, Levet Beker, 427–436 (2023)

DOI

An ultra-compact and wireless tag for battery-free sweat glucose monitoring, Biosensors and Bioelectronics

Abstract

Glucose monitoring before, during, and after exercise is essential for people with diabetes as exercise increases the risk of activity-induced hyper- and hypo-glycemic events. The situation is even more challenging for athletes with diabetes as they have impaired metabolic control compared to sedentary individuals. In this regard, a compact and noninvasive wearable glucose monitoring device that can be easily worn is critical to enabling glucose monitoring. This report presents an ultra-compact glucose tag with a footprint and weight of 1.2 cm2 and 0.13 g, respectively, for sweat analysis. The device comprises a near field communication (NFC) chip, antenna, electrochemical sensor, and microfluidic channels implemented in different material layers. The device has a flexible and conformal structure and can be easily attached to different body parts. The battery-less operation of the device was enabled by NFC-based wireless power transmission and the compact antenna. Femtosecond laser ablation was employed to fabricate a highly compact and flexible NFC antenna. The proposed device demonstrated excellent operating characteristics with a limit of detection (LOD), limit of quantification (LOQ), and sensitivity of 24 μM, 74 μM, and 1.27 μA cm−2 mM−1, respectively. The response of the proposed sensor in sweat glucose detection and quantification was validated by nuclear magnetic resonance spectroscopy (NMR). Also, the device’s capability in attachment to the body, sweat collection, and glucose measurement was demonstrated through in vitro and in vivo experiments, and satisfactory results were obtained.

Hadi Mirzajani, Taher Abbasiasl, Fariborz Mirlou, Emin Istif, Mohammad Javad Bathaei, Çağdaş Dağ, Oğuzhan Deyneli, Dilek Yazıcı, Levent Beker,213, 2022

DOI

A Wearable Paper-Integrated Microfluidic Device for Sequential Analysis of Sweat Based on Capillary Action.

Abstract

Soft, skin-mounted microfluidic devices can collect microliter volumes of eccrine sweat and are capable of in situ real-time analysis of different biomarkers to assess physiological state and health. Chrono-analysis of sweat can be implemented to monitor temporal variations of biomarker concentrations over a certain period of interest. Conventional methods used to capture sweat or some of the newly developed microfluidic platforms for sweat collection and analysis are based on absorbent pads. They suffer from evaporation, leading to considerable deviations in the concentration of the biomarkers. Here, a paper-integrated microfluidic device is presented for sequential analysis of sweat that is easy to fabricate and does not include air exits for each reservoir, which reduces undesirable effects of sweat evaporation. Furthermore, the high capillary force of filter paper is leveraged to route the liquid into the chambers in a sequential fashion and allow further chemical analysis. The employed design of the paper-embedded microfluidic device successfully samples and analyzes artificial sweat sequentially for flow rates up to 5 μL min−1 without showing any leakage. We demonstrated the performance of the device, employing colorimetric assays for chrono-analysis of glucose standard solutions at concentrations in the range of 10–100 mM and pH of sweat during exercise. The results reveal the presented approach’s functionality and potential to analyze the concentration of biomarkers over a certain period sequentially.

Abbasiasl, T., Mirlou, F., Istif, E., Koydemir, H. C., & Beker, L. (2022).
Biomolecular solution X-ray scattering at n2STAR Beamline

Abstract

Small angle X-ray Scattering (SAXS) is a method for determining basic structural characteristics such as size, shape, and surface of particles. SAXS can generate low resolution models of biomolecules faster than any other conventional structural biology tools. SAXS data is mostly collected in synchrotron facilities to obtain the best scattering data possible however home source SAXS devices can also generate valuable data when optimized properly. Here, we examined sample data collection and optimization at home source SAXS beamline in terms of concentration, purity, and the duration of data acquisition. We validated that high concentration, monodisperse and ultra pure protein samples obtained by size exclusion chromatography are necessary for generating viable SAXS data using home source beamline. Longer data collection time does not always generate higher resolutions but at least one hour is required for generating a feasible model from SAXS data. Furthermore, with small optimizations both during data collection and later data analysis SAXS can determine properties such as oligomerization, molecular mass, and overall shape of particles in solution under physiological conditions.

Oktay Göcenler, Cansu M. Yenici, Kerem Kahraman, Cengizhan Büyükdağ, Çağdaş Dağ,

DOI

Use of an elastic buffer layer for improved performance of a polymer microcylinder ring resonator hydrogen sensor, Sensors and Actuators B: Chemical

Abstract

The impact of substrate on Pd nanofilm expansion in a Pd-H2 system is investigated using polymer microcylinder ring resonator (PMRR) platform. Being a highly sensitive platform for H2 gas detection, PMRR comprises of an inner sensitive Pd nanofilm and an outer PDMS layer coated on a standard optical fiber. Optical whispering gallery modes (WGMs) are excited in the rim of the outermost PDMS layer through evanescent field of a tapered fiber. H2 molecules penetrating the H2-sensitive Pd nanofilm through the PDMS layer cause reversible expansion in the PMRR. This translates into shifts in spectral positions of the WGMs that are observed with tapered fiber transmission spectroscopy. Two types of PMRRs were fabricated. In the first type, Pd nanofilm was directly deposited on the silica surface of an optical fiber. In the other one, a PDMS buffer layer was precoated between Pd nanofilm and the silica surface, with different thicknesses. It is demonstrated that, the use of a PDMS buffer layer yields higher radial expansion of the nanofilm during the interaction with H2 gas. A 180-nm-thick Pd nanofilm coated on ∼2.5-μm-thick PDMS buffer layer showed at least 18% higher radial expansion compared to the case without buffer layer. Identical thickness of Pd nanofilm on a ∼3.5-μm-thick PDMS buffer layer showed 30% higher radial expansion. Numerical and analytical calculations were also performed confirming the experimental results. Among mechanical properties of the PDMS buffer layer, Poisson’s ratio was found to be the most significant parameter affecting the expansion of the nanofilm.

Nima Bavili, Basit Ali, Berna Morova, B. Erdem Alaca, Alper Kiraz

DOI

Activity-Based Photosensitizers with Optimized Triplet State Characteristics Toward Cancer Cell Selective and Image Guided Photodynamic Therapy. ACS Applied Bio Materials

Abstract

Activity-based theranostic photosensitizers are highly attractive in photodynamic therapy as they offer enhanced therapeutic outcome on cancer cells with an imaging opportunity at the same time. However, photosensitizers (PS) cores that can be easily converted to activity-based photosensitizers (aPSs) are still quite limited in the literature. In this study, we modified the dicyanomethylene-4H-chromene (DCM) core with a heavy iodine atom to get two different PSs (DCMO-I, I-DCMO-Cl) that can be further converted to aPS after simple modifications. The effect of iodine positioning on singlet oxygen generation capacity was also evaluated through computational studies. DCMO-I showed better performance in solution experiments and further proved to be a promising phototheranostic scaffold via cell culture studies. Later, a cysteine (Cys) activatable PS based on the DCMO-I core (DCMO-I-Cys) was developed, which induced selective photocytotoxicity along with a fluorescence turn-on response in Cys rich cancer cells.

Kilic, E., Elmazoglu, Z., Almammadov, T., Kepil, D., Etienne, T., Marion, A., … & Kolemen, S

DOI

Development of a cysteine responsive chlorinated hemicyanine for image-guided dual phototherapy

Abstract

A cysteine (Cys) activatable chlorinated hemicyanine (Cl-Cys) was introduced as a tumour selective image-guided dual phototherapy agent. Cl-Cys exhibited a significant turn on response in its near-IR emission signal and activated its singlet oxygen generation as well as photothermal conversion potentials upon reacting with Cys. The laser irradiation of Cl-Cys induced significant cell death in cancer cells with high Cys level, while it stayed deactivated and non-emissive in a healthy cell line. A profound synergistic PDT/PTT effect was observed at high doses. Remarkably, Cl-Cys marks the first ever example of Cys-responsive small organic-based therapeutic agent and holds a great promise to develop new activity-based photosensitizers for dual phototherapy action.

Savani, S., Onbasli, K., Gunduz, H., Aydındogan, E., Erkısa, M., Muti, A., … & Kolemen, S.

DOI

A responsive AIE-active fluorescent probe for visualization of acetylcholinesterase activity in vitro and in vivo. Materials Chemistry Frontiers

Abstract

Acetylcholinesterase (AChE) is a significant enzyme, which plays critical roles in numerous physiological and pathological processes. Thus, selective, and sensitive real-time imaging of AChE activity in vivo has great importance to further understand its contribution to cellular activities and to develop diagnostic tools for several disease states including neurodegenerative disorders and cancer. To this end, we introduced an AChE selective light up fluorescent probe (TCFPB-AChE) with aggregation induced emission (AIE) characteristics to visualize AChE activity both in vitro and in vivo. TCFPB-AChE displayed a selective turn-on fluorescence response upon addition of AChE with a very low detection limit. TCFPB-AChE was further used to image endogenous AChE activity in a glioblastoma cell line and Alzheimer’s disease mice brain tissue with a high signal to noise ratio. In addition to these, the probe was also utilized to visualize varying concentrations of AChE in living mice brains in vivo. Remarkably, TCFPB-AChE marks the first ever example of an AChE responsive AIE-based fluorescent probe.

Xiang, C., Dirak, M., Luo, Y., Peng, Y., Cai, L., Gong, P., … & Kolemen, S.

DOI

Ternary nanocomposites of mesoporous graphitic carbon nitride/black phosphorus/gold nanoparticles (mpg-CN/BP-Au) for photocatalytic hydrogen evolution and electrochemical sensing of paracetamol

Abstract

We report herein the fabrication of a novel ternary nanocomposite of mesoporous graphitic carbon nitride/black phosphorus-gold nanoparticles (mpg-CN/BP-Au) and its catalytic performance in the photocatalytic hydrogen evolution reaction (HER) and electrochemical detection of paracetamol. The photocatalytic hydrogen production rate of mpg-CN/BP-Au nanocomposite (1024 µmol g−1 for 8 h) is compared with mpg-CN, mpg-CN/BP and mpg-CN/Au in the presence of triethanolamine (TEOA) as a hole scavenger under the visible light. In addition to the photocatalytic HER application, as-prepared mpg-CN/BP-Au nanocomposite was deposited on modified glassy carbon electrode (mpg-CN/BP-Au/GCE) and for the first time tested for the detection of paracetamol (PA). Under the optimum conditions, linear range of paracetamol detection was found to be in the range of 0.3–120 µM with a detection limit of 0.0425 µM. mpg-CN/BP-Au/GCE provided higher electrocatalytic activity than pristine mpg-CN and all other tested binary nanocomposites. The enhanced photo- and electrochemical activity of mpg-CN/BP-Au/GCE are attributed to formation of heterojunction between BP and mpg-CN materials. Additionally, Au nanoparticles increase the rate of adsorption of mpg-CN/BP due to the excellent electrical properties and spillover effect. We believe that the presented design and catalysis of the ternary nanocomposite will pave a way in many photo- and electrochemical applications.

Gizem Yanalak, Fatmanur Doganay, Zafer Eroglu, Huseyin Kucukkececi, Emre Aslan, Mustafa Ozmen, Salih Zeki Bas, Onder Metin, Imren Hatay Patir

DOI

Unveiling the catalytic nature of palladium-N-heterocyclic carbene catalysts in the α-alkylation of ketones with primary alcohols

Abstract

We report herein the synthesis of four new Pd-PEPPSI complexes with backbone-modified N-heterocyclic carbene (NHC) ligands and their application as catalysts in the α-alkylation of ketones with primary alcohols using a borrowing hydrogen process and tandem Suzuki–Miyaura coupling/α-alkylation reactions. Among the synthesized Pd-PEPPSI complexes, complex 2c having 4-methoxyphenyl groups at the 4,5-positions and 4-methoxybenzyl substituents on the N-atoms of imidazole exhibited the highest catalytic activity in the α-alkylation of ketones with primary alcohols (18 examples) with yields reaching up to 95%. Additionally, complex 2c was demonstrated to be an effective catalyst for the tandem Suzuki–Miyaura-coupling/α-alkylation of ketones to give biaryl ketones with high yields. The heterogeneous nature of the present catalytic system was verified by mercury poisoning and hot filtration experiments. Moreover, the formation of NHC-stabilized Pd(0) nanoparticles during the α-alkylation reactions was identified by advanced analytical techniques.

Ovezova M, Eroğlu Z, Metin Ö, Çetinkaya B, Gülcemal S

DOI

Expanding the Scope of 2D Black Phosphorus Catalysis to the Near-Infrared Light Initiated Free Radical Photopolymerization

Abstract

In the drive toward the development of efficient and stable inorganic semiconductor materials with broadband solar absorption ability to induce various photochemical processes is a highly attractive research field. In this study, two-dimensional (2D) few-layer black phosphorus (BP) exfoliated in a solvent is utilized as photocatalyst to initiate the polymerization of various monomers under visible and near-IR (NIR) light irradiation. Upon the light exposure, few-layer BP generates excited electrons and holes, which undergo electron transfer reactions with the onium salts to form free radicals capable of initiating free radical polymerization. Among the onium salts tested, aryldiazonium salt was found to be the most efficient in the photopolymerization process owing to its favorable reduction potential with the conduction edge potential of BP. The presented strategy also provides the possibility for the in situ preparation of BP-polymer composite materials.

Kocaarslan A, Eroglu Z, Yilmaz G, Metin O, Yagci Y

DOI

TRACT revisited: an algebraic solution for determining overall rotational correlation times from cross-correlated relaxation rates

Abstract

Accurate rotational correlation times (τcτc) are critical for quantitative analysis of fast timescale NMR dynamics. As molecular weights increase, the classic derivation of τcτc using transverse and longitudinal relaxation rates becomes increasingly unsuitable due to the non-trivial contribution of remote dipole–dipole interactions to longitudinal relaxation. Derivations using cross-correlated relaxation experiments, such as TRACT, overcome these limitations but are erroneously calculated in 65% of the citing literature. Herein, we developed an algebraic solutions to the Goldman relationship that facilitate rapid, point-by-point calculations for straightforward identification of appropriate spectral regions where global tumbling is likely to be dominant. The rigid-body approximation of the Goldman relationship has been previously shown to underestimate TRACT-based rotational correlation time estimates. This motivated us to develop a second algebraic solution that employs a simplified model-free spectral density function including an order parameter term that could, in principle, be set to an average backbone S2 ≈ 0.9 to further improve the accuracy of τcτc estimation. These solutions enabled us to explore the boundaries of the Goldman relationship as a function of the H–N internuclear distance (rr), difference of the two principal components of the axially-symmetric 15N CSA tensor (ΔδNΔδN), and angle of the CSA tensor relative to the N–H bond vector (θθ). We hope our algebraic solutions and analytical strategies will increase the accuracy and application of the TRACT experiment.

Robson, S.A., Dağ, Ç., Wu, H.

DOI

Effectiveness of different types of mask in aerosol dispersion in SARS-CoV-2 infection

Abstract

Objective: To compare the effectiveness of different mask types in limiting the dispersal of coughed air.

Method: The Schlieren method with a single curved mirror was used in this study. Coughed air has a slightly higher temperature than ambient air, which generates a refractive index gradient. A curved mirror with a radius of curvature of 10 m and a diameter of 60 cm was used. The spread of the cough wavefront was investigated among five subjects wearing: (1) no mask; (2) a single surgical mask; (3) a double surgical mask; (4) a cloth mask; (5) a valveless N95 mask; and (6) a valved N95 mask.

Results: All mask types reduced the size of the contaminated region significantly. The percentage reduction in the cross-sectional area of the contaminated region for the same mask types on different subjects revealed by normalized data suggests that the fit of a mask plays an important role.

Conclusions: No significant difference in the spread of coughed air was found between the use of a single surgical mask or a double surgical mask. Cloth masks may be effective, depending on the quality of the cloth. Valved N95 masks exclusively protect the user. The fit of a mask is an important factor to minimize the contaminated region.

Gokhan Tanisali, Ahmet Sozak, Abdul Samet Bulut, Tolga Ziya Sander, Ozlem Dogan, Çağdaş Dağ, Mehmet Gönen, Fusun Can, Hasan DeMirci, Onder Ergonul

DOI

Near-physiological-temperature serial crystallography reveals conformations of SARS-CoV-2 main protease active site for improved drug repurposing

Summary

The COVID-19 pandemic has resulted in 198 million reported infections and more than 4 million deaths as of July 2021 (covid19.who.int). Research to identify effective therapies for COVID-19 includes: (1) designing a vaccine as future protection; (2) de novo drug discovery; and (3) identifying existing drugs to repurpose them as effective and immediate treatments. To assist in drug repurposing and design, we determine two apo structures of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) main protease at ambient temperature by serial femtosecond X-ray crystallography. We employ detailed molecular simulations of selected known main protease inhibitors with the structures and compare binding modes and energies. The combined structural and molecular modeling studies not only reveal the dynamics of small molecules targeting the main protease but also provide invaluable opportunities for drug repurposing and structure-based drug design strategies against SARS-CoV-2.

Serdar Durdagi, Çağdaş Dağ, Berna Dogan, Merve Yigin

DOI

Structural insight into host plasma membrane association and assembly of HIV-1 matrix protein

Abstract

Oligomerization of Pr55Gag is a critical step of the late stage of the HIV life cycle. It has been known that the binding of IP6, an abundant endogenous cyclitol molecule at the MA domain, has been linked to the oligomerization of Pr55Gag. However, the exact binding site of IP6 on MA remains unknown and the structural details of this interaction are missing. Here, we present three high-resolution crystal structures of the MA domain in complex with IP6 molecules to reveal its binding mode. Additionally, extensive Differential Scanning Fluorimetry analysis combined with cryo- and ambient-temperature X-ray crystallography and GNM-based transfer entropy calculations identify the key residues that participate in IP6 binding. Our data provide novel insights about the multilayered HIV-1 virion assembly process that involves the interplay of IP6 with PIP2, a phosphoinositide essential for the binding of Pr55Gag to membrane. IP6 and PIP2 have neighboring alternate binding sites within the same highly basic region (residues 18–33). This indicates that IP6 and PIP2 bindings are not mutually exclusive and may play a key role in coordinating virion particles’ membrane localization. Based on our three different IP6-MA complex crystal structures, we propose a new model that involves IP6 coordination of the oligomerization of outer MA and inner CA domain’s 2D layers during assembly and budding.

Ciftci, H., Tateishi, H., Koiwai, K.

DOI

Effect of Polymer Topology on Microstructure, Segmental Dynamics, and Ionic Conductivity in PEO/PMMA-Based Solid Polymer Electrolytes

Abstract

Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) have attracted much interest due to their high ionic conductivity resulting from inherently fast segmental dynamics and high salt solubility, yet they lack mechanical stability in their neat form. Blending PEO with another rigid, or high glass transition temperature, polymer is a versatile way to improve the mechanical stability; however, the ionic conductivity is strongly reduced due to slower segmental dynamics of highly interpenetrating linear polymer chains. In this work, we used model PEO/PMMA blend systems prepared with various well-defined PEO architectures (linear, stars, hyperbranched, and bottlebrushes) doped with lithium bis(trifluoromethane-sulfonyl)-imide (LiTFSI) and investigated, for the first time, the role of macromolecular architecture of PEO on crystallization, segmental dynamics, and ionic conductivity in the blends and electrolytes. The results suggest that room-temperature miscibility of these polymers can be dramatically extended by using nonlinear PEO in the blends instead of linear chains, which crystallize above 35 wt %. The broadband dielectric spectroscopy results revealed enhanced decoupling of PMMA and PEO segmental dynamics in compact branched architectures, which helps to achieve faster segmental motion of star PEO in glassy PMMA. This manifests as nearly three-fold higher ionic conductivity in these nonlinear blends compared to the conventional linear PEO/PMMA system. Regardless of the PEO architectures, the temperature dependence of ionic conductivity blends with PMMA and LiTFSI is well defined using the Vogel–Fulcher–Tammann mechanism, suggesting that ion transport is mainly affected by the segmental motion. The activation energy values decrease with the increasing ionic conductivity. Overall, our results show that macromolecular architecture can be a tool to decouple segmental dynamics and ion mobility to rationally design SPEs with improved performance.

Recep Bakar, Saeid Darvishi, Tianyu Li, Mertcan Han, Umut Aydemir, Sedat Nizamoglu, Kunlun Hong, and Erkan Senses

DOI

Dual Laser Activatable Brominated Hemicyanine as a Highly Efficient and Photostable Multimodal Phototherapy Agent

Abstract

Dual phototherapy agents have attracted great interest in recent years as they offer enhanced cytotoxicity on cancer cells due to the synergistic effect of photodynamic and photothermal therapies (PDT/PTT). In this study, we demonstrate a brominated hemicyanine (HC-1), which is previously shown as mitochondria targeting PDT agent, can also serve as an effective photosensitizer for PTT for the first time under a single (640 nm or 808 nm) and dual laser (640 nm + 808 nm) irradiation. Generation of reactive oxygen species and photothermal conversion as a function of irradiation wavelength and power were studied. Both single wavelength irradiations caused significant phototoxicity in colon and cervical cancer cells after 5 min of irradiation. However, co-irradiation provided near-complete elimination of cancer cells due to synergistic action. This work introduces an easily accessible small molecule-based synergistic phototherapy agent, which holds a great promise towards the realization of local, rapid and highly efficient treatment modalities against cancer.

Gunduz, H.; Bilici, K.; Cetin, S.; Muti, A.; Sennaroglu, A.*; Acar, H. Y*.; Kolemen, S.

DOI

A Hydrogen Peroxide Responsive Resorufin-Based Phototheranostic Agent for Selective Treatment of Cancer Cells

Abstract

Enhanced selectivity towards cancer cells is one of the most essential features sought in new generation photodynamic therapy (PDT) agents in order to minimize the side effects on healthy cells and to improve the efficacy of the treatment. In this direction, one promising approach is to design activatable photosensitizers, which tend to stay in an OFF state and get activated only in cancer cells with tumor-associated stimuli. Based on this idea, herein we introduced a hydrogen peroxide (H2O2) activatable iodinated resorufin (RR-1) as a red-shifted, water soluble and cancer cell selective photosensitizer. RR-1 exhibited high singlet oxygen quantum yield in aqueous solutions upon reacting with H2O2 and induced selective photocytotoxicity in colorectal (HCT-116) and triple negative breast (MDA MB-231) cancer cells, which contain high level of reactive oxygen species (ROS). Additionally, fluorescence signal of the iodo-resorufin core was restored upon cleavage of the cage unit in these cancer cells. In contrast, very low photocytotoxicity and negligible fluorescence enhancement were observed in normal fibroblast (NIH-3T3) cells. RR-1 not only marks the first example of a H2O2 activatable resorufin-based photosensitizer but also represents the first ever resorufin-based theranostic agent. We anticipate that iodo-resorufin scaffold can be easily modified with different masking units towards realization of highly selective and efficient phototheranostic agents for treatment of various cancer cells.

Almammadov, T.; Kolemen, S.

DOI

A Near-infrared Benzothiazole-based Chemodosimeter for Rapid and Selective Detection of Hydrogen Sulfide

Abstract

Hydrogen sulfide (H2S) is a biologically relevant gaseous molecule, which involves in a wide variety of physiological and pathological processes. Thus, detection of H2S is highly valuable in order to clarify its complex roles. In this study, a new benzothiazole-based donor-acceptor type H2S selective chemodosimeter (HP-1) was synthesized and its H2S detection capabilities were investigated in aqueous solutions. HP-1 exhibited a red-shifted absorption signal at 530 nm and a near-infrared (NIR) fluorescence peak at 680 nm as a result of enhanced intramolecular charge transfer (ICT) in the presence of H2S, which enabled a selective and very rapid ratiometric fluorescent detection. HP-1 was also showed to be highly sensitive toward H2S with a very low limit of detection value.

Kolemen, S.

DOI

Balanced Intersystem Crossing in Iodinated Silicon-Fluoresceins Allows New Class of Red Emissive Theranostic Agents

Abstract

Iodination of the silicon-fluorescein core revealed a new class of highly cytotoxic, red-shifted and water-soluble photosensitizer (SF-I) which is also fairly emissive to serve as a theranostic agent. Singlet oxygen generation capacity of SF-I was evaluated chemically, and up to 45% singlet oxygen quantum yield was reported in aqueous solutions. SF-I was further tested in triple negative breast (MDA MB-231) and colon (HCT-116) cancer cell lines, which are known to have limited chemotherapy options as well as very poor prognosis. SF-I induced efficient singlet oxygen generation and consequent photocytotoxicity in both cell lines upon light irradiation with a negligible dark toxicity while allowing cell imaging at the same time. SF-I marks the first ever example of a silicon xanthene-based photosensitizer and holds a lot of promise as a small-molecule-based theranostic scaffold.

Cetin, S.; Elmazoglu, Z.; Karaman, O.; Gunduz, H.; Gunbas, G*.; Kolemen, S.

DOI

A Leucine Aminopeptidase Activatable Photosensitizer for Cancer Cell Selective Photodynamic Therapy Action

Abstract

Activity based photosensitizers (PS) continue to attract great attention as they enable selective photodynamic therapy action on cancer cells while sparing normal cells even under light irradiation. Sensitivity to specific enzymes that are differentially overexpressed in cancer cells is crucial in the design of activatable PSs. In this direction, we report here, for the first time, a leucine aminopeptidase (LAP) activatable PDT agent (HCL), which is a red-shifted, water soluble and photostable brominated hemicyanine derivative. HCL was activated by endogenous LAP enzyme selectively in A549 (lung) and HCT116 (colon) cancer cells containing high LAP levels and induced effective photocytotoxicity with negligible dark toxicity. Furthermore, the fluorescence of the parent bromo-hemicyanine core was restored upon LAP-based activation in cancer cells. On the other side, no remarkable phototoxicity or fluorescence turn-on was detected in healthy L929 cells. Thus, HCL serves as an effective and tumour associated LAP-sensitive phototheranostic agent. We believe different cancer-associated analytes can be utilized in combination with near-IR absorbing scaffolds in the scope of activatable PDT designs to enrich the tumour-selective PS arsenal.

Arslan, B.; Bilici, K.;* Durmaz, G.; Almammadov, T.; Khan, M.; Sennaroglu, A.; Yagci Acar, H.; Kolemen,

DOI

An easily available reaction-based ratiometric AIE probe for lysosomal-targeted visualization of hydrogen polysulfides in acute ulcerative colitis

Abstract

Hydrogen polysulfide (H2Snn >1), as a direct oxidizing form of hydrogen sulfide, is closely associated with intestinal diseases such as ulcerative colitis (UC). A probe that can selectively detect H2Sn in the pathological environment of UC is in urgent demand. Ratiometric probes are powerful in the quantitative detection of H2Sn in living organisms. Herein, we developed a ratiometric fluorescent probe TCFPB–H2Sn for selective detection of H2Snin vitro and in vivo. Significantly, TCFPB–H2Sn demonstrated a fast, sensitive and specific detection performance for H2Sn, and has excellent lysosomal targeting ability and aggregation-induced emission (AIE) characteristics. More importantly, TCFPB–H2Sn was the first probe to achieve endogenous H2Sn imaging in acute ulcerative colitis successfully.

Xiang, C.; Li, C.; Xiang, J.; Luo, Y.; Peng, J.; Wang, J.; Kolemen, S.; Zhang, P.; Gong, P.; Cai, L.

DOI

2022
Hadi Mirzajani, Taher Abbasiasl, Fariborz Mirlou, Emin Istif, Mohammad Javad Bathaei, Çağdaş Dağ, Oğuzhan Deyneli, Dilek Yazıcı, Levent Beker,
An ultra-compact and wireless tag for battery-free sweat glucose monitoring, Biosensors and Bioelectronics, 213, 2022
Abbasiasl, T., Mirlou, F., Istif, E., Koydemir, H. C., & Beker, L. (2022). A Wearable Paper-Integrated Microfluidic Device for Sequential Analysis of Sweat Based on Capillary Action. Sensors & Diagnostics. 10.1039/D2SD00032F
Oktay GöcenlerCansu M. YeniciKerem KahramanCengizhan BüyükdağÇağdaş Dağ, Biomolecular solution X-ray scattering at n2STAR Beamline,
Nima Bavili, Basit Ali, Berna Morova, B. Erdem Alaca, Alper Kiraz, Use of an elastic buffer layer for improved performance of a polymer microcylinder ring resonator hydrogen sensor, Sensors and Actuators B: Chemical, 358, 2022
Kilic, E., Elmazoglu, Z., Almammadov, T., Kepil, D., Etienne, T., Marion, A., … & Kolemen, S. (2022). Activity-Based Photosensitizers with Optimized Triplet State Characteristics Toward Cancer Cell Selective and Image Guided Photodynamic Therapy. ACS Applied Bio Materials.
Savani, S., Onbasli, K., Gunduz, H., Aydındogan, E., Erkısa, M., Muti, A., … & Kolemen, S. (2022). Development of a cysteine responsive chlorinated hemicyanine for image-guided dual phototherapy. Bioorganic Chemistry122, 105725.
Xiang, C., Dirak, M., Luo, Y., Peng, Y., Cai, L., Gong, P., … & Kolemen, S. (2022). A responsive AIE-active fluorescent probe for visualization of acetylcholinesterase activity in vitro and in vivo. Materials Chemistry Frontiers.
2021
Gizem Yanalak, Fatmanur Doganay, Zafer Eroglu, Huseyin Kucukkececi, Emre Aslan, Mustafa Ozmen, Salih Zeki Bas, Onder Metin, Imren Hatay Patir,
Ternary nanocomposites of mesoporous graphitic carbon nitride/black phosphorus/gold nanoparticles (mpg-CN/BP-Au) for photocatalytic hydrogen evolution and electrochemical sensing of paracetamol,
Applied Surface Science, 557,2021
Ovezova M, Eroğlu Z, Metin Ö, Çetinkaya B, Gülcemal S. Unveiling the catalytic nature of palladium-N-heterocyclic carbene catalysts in the α-alkylation of ketones with primary alcohols. Dalton Trans. 2021 Aug 21;50(31):10896-10908.
Kocaarslan A, Eroglu Z, Yilmaz G, Metin O, Yagci Y. Expanding the Scope of 2D Black Phosphorus Catalysis to the Near-Infrared Light Initiated Free Radical Photopolymerization. ACS Macro Lett. 2021 Jun 15;10(6):679-683.
Robson, S.A., Dağ, Ç., Wu, H. et al. TRACT revisited: an algebraic solution for determining overall rotational correlation times from cross-correlated relaxation rates. J Biomol NMR 75, 293–302 (2021).
Gokhan Tanisali, Ahmet Sozak, Abdul Samet Bulut, Tolga Ziya Sander, Ozlem Dogan, Çağdaş Dağ, Mehmet Gönen, Fusun Can, Hasan DeMirci, Onder Ergonul,
Effectiveness of different types of mask in aerosol dispersion in SARS-CoV-2 infection,International Journal of Infectious Diseases, 109,2021
Serdar Durdagi, Çağdaş Dağ, Berna Dogan, Merve Yigin,et al. Near-physiological-temperature serial crystallography reveals conformations of SARS-CoV-2 main protease active site for improved drug repurposing, Structure, 29, 12,2021
Ciftci, H., Tateishi, H., Koiwai, K. et al. Structural insight into host plasma membrane association and assembly of HIV-1 matrix protein. Sci Rep 11, 15819 (2021).
Recep Bakar, Saeid Darvishi, Tianyu Li, Mertcan Han, Umut Aydemir, Sedat Nizamoglu, Kunlun Hong, and Erkan Senses Effect of Polymer Topology on Microstructure, Segmental Dynamics, and Ionic Conductivity in PEO/PMMA-Based Solid Polymer Electrolytes ACS Applied Polymer Materials 2022 4 (1), 179-190
Gunduz, H.; Bilici, K.; Cetin, S.; Muti, A.; Sennaroglu, A.*; Acar, H. Y*.; Kolemen, S.* “Dual Laser Activatable Brominated Hemicyanine as a Highly Efficient and Photostable Multimodal Phototherapy Agent” J. Photochem. Photobiol. B: Biology 2021, 217, 112171.
Cetin, S.; Elmazoglu, Z.; Karaman, O.; Gunduz, H.; Gunbas, G*.; Kolemen, S.* “Balanced Intersystem Crossing in Iodinated Silicon-Fluoresceins Allows New Class of Red Emissive Theranostic Agents” ACS Med. Chem. Lett. 2021, 12, 752-757.
Almammadov, T.; Kolemen, S.* “A Hydrogen Peroxide Responsive Resorufin-Based Phototheranostic Agent for Selective Treatment of Cancer Cells” Dyes Pigm. 2021, 193, 109499.
Kolemen, S.* “A Near-infrared Benzothiazole-based Chemodosimeter for Rapid and Selective Detection of Hydrogen Sulfide” JOTCSA 2021, 8, 567-578.
Arslan, B.; Bilici, K.;* Durmaz, G.; Almammadov, T.; Khan, M.; Sennaroglu, A.; Yagci Acar, H.; Kolemen, S.* “A Leucine Aminopeptidase Activatable Photosensitizer for Cancer Cell Selective Photodynamic Therapy Action” Dyes Pigm., 2021, 195, 109735.
Xiang, C.; Li, C.; Xiang, J.; Luo, Y.; Peng, J.; Wang, J.; Kolemen, S.; Zhang, P.; Gong, P.; Cai, L. “An easily available reaction-based ratiometric AIE probe for lysosomal-targeted visualization of hydrogen polysulfides in acute ulcerative colitis” Mater. Chem. Front., 2021, 5, 7638-7644.